EP1876141B1 - Stable high-temperature borohydride formulation - Google Patents
Stable high-temperature borohydride formulation Download PDFInfo
- Publication number
- EP1876141B1 EP1876141B1 EP07252555A EP07252555A EP1876141B1 EP 1876141 B1 EP1876141 B1 EP 1876141B1 EP 07252555 A EP07252555 A EP 07252555A EP 07252555 A EP07252555 A EP 07252555A EP 1876141 B1 EP1876141 B1 EP 1876141B1
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- EP
- European Patent Office
- Prior art keywords
- borohydride
- sodium
- sbh
- acrylic acid
- alternatively
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Not-in-force
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- 239000000203 mixture Substances 0.000 title claims description 28
- 238000009472 formulation Methods 0.000 title description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 82
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 47
- 239000012279 sodium borohydride Substances 0.000 claims description 47
- 229920002125 Sokalan® Polymers 0.000 claims description 20
- 239000004584 polyacrylic acid Substances 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 17
- 230000002745 absorbent Effects 0.000 claims description 13
- 239000002250 absorbent Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 9
- 150000004692 metal hydroxides Chemical class 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 3
- 229920006037 cross link polymer Polymers 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- 229920003169 water-soluble polymer Polymers 0.000 claims description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 description 23
- 239000000654 additive Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 230000000996 additive effect Effects 0.000 description 15
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 13
- 159000000000 sodium salts Chemical class 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- 229920002873 Polyethylenimine Polymers 0.000 description 7
- 239000000546 pharmaceutical excipient Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229940124531 pharmaceutical excipient Drugs 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920002717 polyvinylpyridine Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000001204 N-oxides Chemical class 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000013011 aqueous formulation Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229940105329 carboxymethylcellulose Drugs 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 1
- -1 hydroxy, amino Chemical group 0.000 description 1
- 239000008011 inorganic excipient Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- HVTHJRMZXBWFNE-UHFFFAOYSA-J sodium zincate Chemical compound [OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Zn+2] HVTHJRMZXBWFNE-UHFFFAOYSA-J 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
- C01B6/10—Monoborane; Diborane; Addition complexes thereof
- C01B6/13—Addition complexes of monoborane or diborane, e.g. with phosphine, arsine or hydrazine
- C01B6/15—Metal borohydrides; Addition complexes thereof
- C01B6/19—Preparation from other compounds of boron
- C01B6/21—Preparation of borohydrides of alkali metals, alkaline earth metals, magnesium or beryllium; Addition complexes thereof, e.g. LiBH4.2N2H4, NaB2H7
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
- C01B6/10—Monoborane; Diborane; Addition complexes thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- This invention relates to an aqueous sodium borohydride mixture having increased stability, especially at high temperatures.
- Aqueous borohydride solutions having relatively good stability are known. For example, solutions containing about 12% sodium borohydride and about 40% sodium hydroxide are sold commercially. In some applications, a stable borohydride-containing solution having less sodium hydroxide is desired, e.g., in hydrogen fuel cells. Such a solution is described in U.S. Pat. No. 6,866,689 ; it contains about 44% sodium borohydride and about 0.2% sodium hydroxide. However, this solution exhibits relatively high rates of borohydride decomposition at elevated temperatures.
- US-A-3 933 676 discloses borohydride with the inorganic excipient sodium zincate.
- the problem addressed by this invention is to find an aqueous formulation of borohydride that has improved stability at elevated temperatures.
- the present invention provides an aqueous mixture comprising: (a) from 15% to 65% of at least one borohydride compound; (b) from 1% to 10% of at least one metal hydroxide; and (c) from 0.1% to 20% of at least one absorbent polymer or excipient.
- the invention is further directed to a method for stabilizing aqueous borohydride mixtures by adding at least one absorbent polymer.
- a "borohydride compound” is a compound containing the borohydride anion, BH 4 -.
- An "absorbent polymer” is a polymer capable of absorbing water.
- absorbent polymers are chosen from among water-soluble polymers (polymers having water solubility of at least 1%, alternatively at least 5%), cellulose and its derivatives, and cross-linked polymers.
- Cross-linked polymers preferably have carboxyl, amide, hydroxy, amino, or ether groups, or a combination thereof, to facilitate dispersion in water.
- Excipients are pharmaceutical excipients as defined, e.g., in Handbook of Pharmaceutical Excipients, A.
- preferred absorbent polymers include polyacrylic acids, polyacrylamide co polyacrylic acid, copolymers of acrylic acid (e.g., polyacrylic acid co polyethylene oxide), polyvinylpyrrolidone, polyvinylpyridine, polyvinylpyridine N-oxide, polyvinylimidazole, ethoxylated polyethylenimine, cellulose esters (e.g., acetate, butyrate), hydroxyalkyl celluloses, and carboxymethyl cellulose.
- the aqueous mixture of the present invention may be a solution, slurry, gel, or any other fluid mixture at temperatures of at least 40°C. Mixtures having higher concentrations of borohydride, e.g., at least 50%, typically are solids or thick slurries at ambient temperature of about 25°C, but become fluid at higher temperatures.
- the amount of borohydride compound(s) is at least 20%, alternatively at least 25%. In one embodiment, the amount of metal hydroxide(s) is no more than 8%, alternatively no more than 6%, alternatively no more than 4%. In one embodiment of the invention, the amount of metal hydroxide is at least 2%, alternatively at least 3%. In one embodiment, the amount of borohydride compound is no more than 55%, alternatively no more than 50%, alternatively no more than 45%, alternatively no more than 40%.
- the borohydride compound is a metal salt which has a metal cation from groups 1, 2, 4, 5, 7, 11, 12 or 13 of the periodic table, or a mixture thereof.
- the borohydride compound is an alkali metal borohydride or combination thereof, alternatively it comprises sodium borohydride (SBH) or potassium borohydride or a mixture thereof, alternatively sodium borohydride.
- the metal hydroxide is an alkali metal hydroxide or combination thereof; alternatively sodium, lithium or potassium hydroxide, or a mixture thereof; alternatively sodium hydroxide or potassium hydroxide; alternatively sodium hydroxide. More than one alkali metal borohydride and more than one metal hydroxide may be present.
- the amount of absorbent polymer(s) is at least 0.2%, alternatively at least 0.4%, alternatively at least 1%, alternatively at least 2%. In one embodiment of the invention, the amount of absorbent polymer(s) is no more than 15%, alternatively no more than 12%, alternatively no more than 10%, alternatively no more than 8%. In one embodiment of the invention, extremely small amounts of absorbent polymer(s) are required; at least 0.1%, but no more than 1%, alternatively no more than 0.5%.
- partially neutralized polyacrylic acids or copolymers containing at least 20% acrylic acid monomer units, alternatively at least 30%, alternatively at least 50%, alternatively at least 75%, may require only very small amounts of absorbent polymer(s) and/or excipient(s).
- the degree of neutralization of the polyacrylic acids added to the borohydride compound(s) is not critical because the aqueous mixture contains additional base, so that the acids typically will be completely neutralized in the aqueous mixture.
- a weight average molecular weight of at least 1500 is preferred, alternatively at least 3000, alternatively at least 5000.
- the aqueous mixture is substantially free of substances that catalyze hydrolysis of borohydride, e.g., salts of transition metals such as Co, Ru, Ni, Fe, Rh, Pd, Os, Ir, Pt, or mixtures thereof; and borides of Co and/or Ni.
- borohydride e.g., salts of transition metals such as Co, Ru, Ni, Fe, Rh, Pd, Os, Ir, Pt, or mixtures thereof; and borides of Co and/or Ni.
- the aqueous mixture of this invention also may be used in the fields of synthesis and metal recovery.
- poly acrylic acid partial cross linked partial sodium salt to higher-concentration sodium borohydride formulations also results in decreasing the hydrolysis rates of the 40 and 50 wt % formulations.
- An unexpected phenomenon has been observed when these formulations are heated for long periods of time. After an initial induction period, the rate of hydrolysis of the borohydride decreases to nearly zero.
- Table 3 Decomposition rate of solutions containing 50 % SBH, 5 % NaOH with additives at room temperature and 58 °C 50 % SBH, 5 %
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Medicinal Preparation (AREA)
- Fuel Cell (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
- This invention relates to an aqueous sodium borohydride mixture having increased stability, especially at high temperatures.
- Aqueous borohydride solutions having relatively good stability are known. For example, solutions containing about 12% sodium borohydride and about 40% sodium hydroxide are sold commercially. In some applications, a stable borohydride-containing solution having less sodium hydroxide is desired, e.g., in hydrogen fuel cells. Such a solution is described in
U.S. Pat. No. 6,866,689 ; it contains about 44% sodium borohydride and about 0.2% sodium hydroxide. However, this solution exhibits relatively high rates of borohydride decomposition at elevated temperatures. -
US-A-3 933 676 discloses borohydride with the inorganic excipient sodium zincate. - The problem addressed by this invention is to find an aqueous formulation of borohydride that has improved stability at elevated temperatures.
- The present invention provides an aqueous mixture comprising: (a) from 15% to 65% of at least one borohydride compound; (b) from 1% to 10% of at least one metal hydroxide; and (c) from 0.1% to 20% of at least one absorbent polymer or excipient. The invention is further directed to a method for stabilizing aqueous borohydride mixtures by adding at least one absorbent polymer.
- Percentages are weight percentages and temperatures are in °C, unless specified otherwise. A "borohydride compound" is a compound containing the borohydride anion, BH4-. An "absorbent polymer" is a polymer capable of absorbing water. Preferably, absorbent polymers are chosen from among water-soluble polymers (polymers having water solubility of at least 1%, alternatively at least 5%), cellulose and its derivatives, and cross-linked polymers. Cross-linked polymers preferably have carboxyl, amide, hydroxy, amino, or ether groups, or a combination thereof, to facilitate dispersion in water. "Excipients" are pharmaceutical excipients as defined, e.g., in Handbook of Pharmaceutical Excipients, A. Wade & P.J. Weller (1964). In one embodiment of the invention, preferred absorbent polymers include polyacrylic acids, polyacrylamide co polyacrylic acid, copolymers of acrylic acid (e.g., polyacrylic acid co polyethylene oxide), polyvinylpyrrolidone, polyvinylpyridine, polyvinylpyridine N-oxide, polyvinylimidazole, ethoxylated polyethylenimine, cellulose esters (e.g., acetate, butyrate), hydroxyalkyl celluloses, and carboxymethyl cellulose. The aqueous mixture of the present invention may be a solution, slurry, gel, or any other fluid mixture at temperatures of at least 40°C. Mixtures having higher concentrations of borohydride, e.g., at least 50%, typically are solids or thick slurries at ambient temperature of about 25°C, but become fluid at higher temperatures.
- In one embodiment, the amount of borohydride compound(s) is at least 20%, alternatively at least 25%. In one embodiment, the amount of metal hydroxide(s) is no more than 8%, alternatively no more than 6%, alternatively no more than 4%. In one embodiment of the invention, the amount of metal hydroxide is at least 2%, alternatively at least 3%. In one embodiment, the amount of borohydride compound is no more than 55%, alternatively no more than 50%, alternatively no more than 45%, alternatively no more than 40%. Preferably, the borohydride compound is a metal salt which has a metal cation from groups 1, 2, 4, 5, 7, 11, 12 or 13 of the periodic table, or a mixture thereof. In one embodiment, the borohydride compound is an alkali metal borohydride or combination thereof, alternatively it comprises sodium borohydride (SBH) or potassium borohydride or a mixture thereof, alternatively sodium borohydride. Preferably, the metal hydroxide is an alkali metal hydroxide or combination thereof; alternatively sodium, lithium or potassium hydroxide, or a mixture thereof; alternatively sodium hydroxide or potassium hydroxide; alternatively sodium hydroxide. More than one alkali metal borohydride and more than one metal hydroxide may be present.
- In one embodiment of the invention, the amount of absorbent polymer(s) is at least 0.2%, alternatively at least 0.4%, alternatively at least 1%, alternatively at least 2%. In one embodiment of the invention, the amount of absorbent polymer(s) is no more than 15%, alternatively no more than 12%, alternatively no more than 10%, alternatively no more than 8%. In one embodiment of the invention, extremely small amounts of absorbent polymer(s) are required; at least 0.1%, but no more than 1%, alternatively no more than 0.5%. For example, partially neutralized polyacrylic acids, or copolymers containing at least 20% acrylic acid monomer units, alternatively at least 30%, alternatively at least 50%, alternatively at least 75%, may require only very small amounts of absorbent polymer(s) and/or excipient(s). The degree of neutralization of the polyacrylic acids added to the borohydride compound(s) is not critical because the aqueous mixture contains additional base, so that the acids typically will be completely neutralized in the aqueous mixture. For polymers used in this invention, a weight average molecular weight of at least 1500 is preferred, alternatively at least 3000, alternatively at least 5000.
- In one embodiment of the invention, the aqueous mixture is substantially free of substances that catalyze hydrolysis of borohydride, e.g., salts of transition metals such as Co, Ru, Ni, Fe, Rh, Pd, Os, Ir, Pt, or mixtures thereof; and borides of Co and/or Ni.
- The aqueous mixture of this invention also may be used in the fields of synthesis and metal recovery.
-
Table 1: Decomposition rate of solutions containing 25% SBH, 3% NaOH with additives at room temperature and 60 °C. 25% SBH, 3% NaOH with Additive Wt % of additive Rate of decomposition At RT, %SBH/day Rate of decomposition at 60 °C %SBH/day % decrease in decomposition rate at 60 °C None, 25 % NaBH4 , 3 % NaOH N/A -0.12 -0.958 N/A Poly acrylic acid partial sodium salt, lightly cross linked (solid) CAS # 76774-25-9 0.5 -0.05 -0.564 41 Poly acrylamide co acrylic acid partial sodium salt (solid) Mw=15,000,000 0.5 -0.074 -0.662 31 Poly acrylic acid co poly ethylene oxide (solid) CAS # 27599-59-56-0 0.5 -0.012 -0.614 36 Poly vinyl pyrrolidone (solid) Mw=10,000; CAS # 9003-39-0 0.5 -0.004 -0.734 23 Carboxy methyl cellulose sodium salt (solid) Mw=70,000; CAS # 9004-39-4 0.5 -0.032 -0.728 24 - The addition of poly acrylic acid partial cross linked partial sodium salt to higher-concentration sodium borohydride formulations also results in decreasing the hydrolysis rates of the 40 and 50 wt % formulations. An unexpected phenomenon has been observed when these formulations are heated for long periods of time. After an initial induction period, the rate of hydrolysis of the borohydride decreases to nearly zero.
Table 2: Decomposition rate ("DR") of solutions containing 40 % SBH, 5 % NaOH with additives at room temperature and 50°C 40 % SBH, 5 % NaOH with Additive Wt % of additive DR at RT %SBH/day DR at 50 °C %SBH/Day % decrease in DR at 50 °C DR at 50 °C %SBH/Day After induction period None, 40 % NaBH4 , 5 % NaOH N/A 0.0549 0.3604 N/A N/A Poly acrylic acid partial sodium salt, lightly cross linked (solid) CAS # 76774-25-9 0.5 0.0333 0.1139 68 0.0547 Poly acrylic acid partial sodium salt (Liquid) Mw= 30,000; CAS # 9003-04-07 4% 0.0339 0.1716 52 0.0084 Table 3: Decomposition rate of solutions containing 50 % SBH, 5 % NaOH with additives at room temperature and 58 °C 50 % SBH, 5 % NaOH with Additive Wt % of additive DR at RT %SBH/day DR at 58°C %SBH/day % decrease in DR DR at 58 °C %SBH/day after induction period None, 50 % NaBH4, 5 % NaOH N/A 0.0031 0.35 N/A N/A Poly acrylic acid partial sodium salt, lightly cross linked (solid) CAS # 76774-25-9 0.5 % - 0.03121 91 0.01165 Poly acrylic acid partial sodium salt (Liquid) Mw= 30,000; CAS # 9003-04-07 4 % - 0.01715 95 0.01388 Table 4: Decomposition rate of solutions containing 25 % SBH, 5 % NaOH with different wt % of poly acrylic acid), partial sodium salt solid at 22 °C. Temp °C Wt % additive Rate of decomposition % SBH/Day % Difference 22 0 0.026 N/A 22 0.5 0.011 57.7 22 1 0.0485 22 1.5 0.0473 22 2 0.0473 22 4 0.025 3.8 Table 5: Decomposition rate of solutions containing 25 % SBH, 5 % NaOH with different wt % of poly acrylic acid), partial sodium salt solid at 60 °C. Temp °C Wt % additive Rate of decomposition % SBH/Day % Difference 60 0 0.4334 N/A 60 0.5 0.3764 13.2 60 1 0.409 5.6 60 1.5 0.424 2.1 60 2 0.4114 5.1 60 4 0.4201 3.1 Table 6: Decomposition rate of solutions containing 25 % SBH, 5 % NaOH with different wt % of poly (acrylic acid sodium salt 30 % in water Mw=15,000 at 22 °C. (wt.% additive in this table, and following tables based on total polymer/water formulation) Temp °C Wt % additive Rate of decomposition, % SBH/Day Rate of decomposition of standard, % SBH/Day % Difference 22 0 22 10 0.1161 0.0114 22 5 0.0019 0.1029 98.1 22 1 0.046 0.0421 Table 7: Decomposition rate of solutions containing 25 % SBH, 5 % NaOH with different wt % of polyacrylic acid sodium salt 30 % in water Mw=15,000 at 60 °C Temp °C Wt% additive Rate of decomposition, % SBH/Day Rate of decomposition of standard, % SBH/Day % Difference 60 0 60 10 0.3982 0.4993 20.2 60 5 0.4301 0.4964 13.3 60 1 0.4236 0.4399 3.7 Table 8: Decomposition rate of solutions containing 25 % SBH, 5 % NaOH with 15 wt % of polyethyleneimine 80 % ethoxylated at 22 °C Temp °C Wt % additive Rate of decomposition % SBH/Day % Difference Standard 0 0.0585 N/A 22 Polyethylenimine 80 %, ethoxylated, 37 % in water Mw= 50,000; CAS # 26558-46-8 15 0.0116 80.1 22 Polyethylenimine 80 % ethoxylated, 35 to 40 % in water Mw= 70,000; CAS # 26558-46-8 15 0.0321 45.1 Table 9: Decomposition rate of solutions containing 25 % SBH, 5 % NaOH with 15 wt % of polyethyleneimine 80 % ethoxylated at 60 °C Temp °C Wt % additive Rate of decomposition % SBH/Day % Difference Standard 0 0.5782 N/A 60 Polyethyleneimine 80 % ethoxylated, 37 % in water M w= 50,000; CAS # 26558-46-8 15 0.5096 11.8 60 Polyethylenimine 80 % ethoxylated , 35 to 40 % in water Mw= 70,000; CAS # 26558-46-8 15 0.5052 12.6 Table 10: Decomposition rate of solutions containing 25 % SBH, 5 % NaOH with 15 wt % of different MW polyacrylic acid sodium salts at 22 °C Temp °C Wt % additive DR %SBH/Day % Difference Standard 0 0.0585 N/A 22 Poly (acrylic acid sodium salt 45 % in water Mw= 1,200; CAS # 9003- 04-7 15 0.06493 Higher by 10 22 Poly (acrylic acid sodium salt 45 % in water Mw= 8,000; CAS # 9003-04-7 15 0.0257 56.0 22 Poly (acrylic acid sodium salt 40 % in water Mw= 30,000; CAS # 9003-04-7 15 0.0091 84.4 Table 11: Decomposition rate of solutions containing 25 % SBH, 5 % NaOH with 15 wt % of different MW poly acrylic acid sodium salts at 60°C Temp °C Wt % additive DR %SBH/Day % Difference Standard 0 0.5782 N/A 60 Poly (acrylic acid sodium salt 45 % in water M w= 1,200; CAS # 9003-04-7 15 0.3812 34.0 60 Poly (acrylic acid sodium salt 45 % in water M w= 8,000; CAS # 9003-04-7 15 0.3607 37.6 60 Poly (acrylic acid sodium salt 40 % in water M w= 30,000; CAS # 9003-04-7 15 0.3736 35.38
Claims (10)
- An aqueous mixture comprising:(a) from 15% to 65% of at least one borohydride compound;(b) from 1% to 10% of at least one metal hydroxide; and(c) from 0.1% to 20% of at least one absorbent polymer.
- The aqueous mixture of claim 1 in which said at least one borohydride compound is sodium borohydride, potassium borohydride or a combination thereof; and said at least one metal hydroxide is sodium, lithium or potassium hydroxide, or a combination thereof.
- The aqueous mixture of claim 2 in which said at least one absorbent polymer is selected from among water-soluble polymers, cellulose and its derivatives and crosslinked polymers.
- The aqueous mixture of claim 3 in which the borohydride compound is sodium borohydride and the base is sodium hydroxide.
- The aqueous mixture of claim 4 having from 2% to 8% sodium hydroxide and from 20% to 50% sodium borohydride.
- The aqueous mixture of claim 5 in which said at least one absorbent polymer is polyacrylic acid or a copolymer of acrylic acid having at least 50% acrylic acid monomer units.
- The aqueous mixture of claim 6 having from 0.1 % to 1% polyacrylic acid or acrylic acid copolymer, and in which weight average molecular weight of the polyacrylic acid or copolymer of acrylic acid is at least 1500.
- A method for stabilizing an aqueous borohydride mixture containing from 15% to 65% of at least one borohydride compound and from 1% to 10% of at least one metal hydroxide; said method comprising adding from 0.1 % to 20% of at least one absorbent polymer.
- The method of claim 8 in which said at least one metal hydroxide is sodium hydroxide and said at least one borohydride compound is sodium borohydride.
- The method of claim 9 in which the aqueous borohydride mixture has from 2% to 8% sodium hydroxide and from 20% to 50% sodium borohydride.
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EP (1) | EP1876141B1 (en) |
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CN101633492B (en) * | 2008-07-22 | 2013-02-27 | 汉能科技有限公司 | Solid hydroboron hydrogen production method and device thereof |
KR101245914B1 (en) * | 2010-12-21 | 2013-03-20 | 황보창수 | Processing device of a dried cuttlefish |
US20170158390A1 (en) * | 2015-12-04 | 2017-06-08 | Mead Johnson Nutrition Company | Powder dosing closure |
JP2019026753A (en) * | 2017-07-31 | 2019-02-21 | 株式会社ブリヂストン | Aldehyde scavenger for polyurethane, polyurethane and method for producing polyurethane |
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US2970114A (en) * | 1958-01-27 | 1961-01-31 | Metal Hydrides Inc | Stabilized aqueous solutions of sodium borohydride |
DE1567554A1 (en) * | 1966-04-02 | 1970-07-09 | Goerrig Dipl Chem Dr Rer Nat D | Solids containing alkali hydroxide hydrate, alkali boronate and optionally catalysts |
US3933676A (en) * | 1974-04-08 | 1976-01-20 | Ventron Corporation | Stabilized aqueous solutions of sodium borohydride |
US5169555A (en) * | 1990-11-09 | 1992-12-08 | Morton International, Inc. | Pulp bleaching solution |
US5354478A (en) * | 1993-06-09 | 1994-10-11 | Morton International, Inc. | Alkali metal borohydride/anionic polymer solutions |
FR2746328B1 (en) * | 1996-03-21 | 1998-05-29 | Stmi Soc Tech Milieu Ionisant | ORGANOMINERAL DECONTAMINATION GEL AND ITS USE FOR THE DECONTAMINATION OF SURFACES |
JP2001019401A (en) * | 1999-07-05 | 2001-01-23 | Seijiro Suda | Hydrogen generating agent and hydrogen generating method utilizing the same |
JP2002201001A (en) * | 2000-12-28 | 2002-07-16 | Toyota Motor Corp | Stabilization method for metal complex hydride water solution |
JP2003146604A (en) * | 2001-11-08 | 2003-05-21 | Sekisui Chem Co Ltd | Compression molding for hydrogen generation and method and device for generating hydrogen using the same |
WO2003042096A1 (en) * | 2001-11-13 | 2003-05-22 | Montgomery Chemicals, Llc | Aqueous borohydride compositions |
JP2004196634A (en) * | 2002-12-20 | 2004-07-15 | Honda Motor Co Ltd | Hydride powder used for hydrogen storing/discharging system |
JP4276854B2 (en) * | 2003-01-30 | 2009-06-10 | ウチヤ・サーモスタット株式会社 | Hydrogen generating material, hydrogen generating method and hydrogen generating apparatus |
CN100384736C (en) * | 2004-10-18 | 2008-04-30 | 罗门哈斯公司 | Method for reducing corrosion in solid sodium hydroxide production |
JP4813790B2 (en) * | 2004-12-03 | 2011-11-09 | セイコーインスツル株式会社 | Hydrogen generator and fuel cell system |
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CN101100286A (en) | 2008-01-09 |
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JP2008013431A (en) | 2008-01-24 |
CN101100286B (en) | 2011-11-16 |
US7648644B2 (en) | 2010-01-19 |
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